Increased longevity of the nitrogen content of soil through improved liquid delivery formulations of nitrification inhibitors designed for urea and manure based fertilizers

ABSTRACT

Increasing longevity of the nitrogen content of soil through improved liquid delivery formulations of nitrification inhibitors. The liquid formulation can also be comprised of nitrification inhibitors and urease inhibitors that are co-dissolved or blended solutions of each These novel formulations are designed to apply to fertilizers, especially urea and manure based fertilizers These delivery formulations provide an environmentally sound and inherently safe solvating system that improves the storage stability of the urease inhibitors by utilizing liquid organic non-water containing solvents, maintain the nitrification inhibitors in solution to storage temperatures of at least 10° C. and provides improved application to fertilizer of nitrification inhibitors. These delivery formulations enable safe storage, transport and subsequent application or blending with urea based or manure based fertilizers that can be applied to soil in either a liquid or granular form to provide improved nitrogen retention in the soil for uptake for plant life.

The present application claims priority under 35 USC 120 and is a continuation of U.S. application Ser. No. 14/702,683 filed May 2, 2015, which in turn claims priority under 35 USC 119(e) to U.S. Provisional Application No. 61/987,761 filed May 2, 2014, the entire contents of all of which are incorporated by reference in their entireties.

FIELD OF INVENTION

The present invention relates to increasing and/or maintaining nitrogen content in soil by administration of an improved liquid formulation. In one embodiment, the liquid formulation comprises nitrification inhibitors. In another embodiment, the liquid formulation comprises nitrification inhibitors and/or urease inhibitors that are co-dissolved or blended solutions of each. In an embodiment, the liquid formulations are designed to be used in conjunction with urea and/or manure based fertilizers.

BACKGROUND OF THE INVENTION

Agriculture currently utilizes fertilizers to deliver the needed nutrients of nitrogen, phosphorus, potassium, sulfur, calcium, and magnesium to plants through the application of fertilizers to the soil. Nitrogen generally is the most yield-limiting and costly nutrient element in crop production. Fertilizers are based on nitrogen content, mainly urea and additional plant nutrients and additives. Fertilizers can either be formulated as man-made products or natural organic based animal manure. Nitrogen is the primary nutrient in fertilizers and urea is the primary nitrogen source in fertilizers. Thus, fertilizers have become one vehicle for increasing the nitrogen content in the soil to assist in maintaining the health, overall quality, growth and yields of many of the plants important to agriculture and to civilization. Nitrogen is usually formulated into fertilizer by one or more of urea and/or ammonium nitrate and/or ammonium sulfate and/or manure and/or ammonium phosphate and/or the like.

Generally, the fertilizer is applied to the soil as either a liquid or a solid. Maintaining a sufficient level of nitrogen concentration in the soil proves difficult over time due to nitrogen and nitrogen containing compounds (such as urea) solubilities in water.

When rain or water run-off contacts the soil, the nitrogen or nitrogen containing compounds may be carried with the water to surrounding water-ways.

Alternatively, the degradation of nitrogen content may be attributed to volatilization (such as for ammonia and NOx where x is 1, 2 or 3) and water runoff due to the better water solubility of nitrites/nitrates. Loss due to volatilization is sometimes driven by a urease enzyme that catalyzes hydrolysis of urea to ammonia and carbon dioxide and to the biological oxidation by soil microbes, such as Nitrosomonas bacteria, of NH3 or NH4 to NOx's such as nitric oxide, an atmospheric greenhouse gas which, on a molecular basis, has 310 times the global warming potential of carbon dioxide. This results in a substantial loss of nitrogen content in the fertilizer impacting costs to the farmer. Moreover, the loss of nitrogen from the soil results not only in water pollution but also atmospheric pollution.

Nitrogen in the soil is also lost by the attack of nitrogen and nitrogen containing compounds (such as urea) by enzymes like the urease enzyme. Attack by the urease enzyme causes urea to degrade to carbon dioxide and ammonia. Biological oxidations by soil microbes, such as Nitrosomonas bacteria, of ammoniacal nitrogen to nitrate nitrogen are also a cause of the diminishing nitrogen content in soil over time. While the conversion of urea to ammonia and oxidation of ammonia to nitrates within the soil is beneficial to plants, conversions occurring on top of the soil, where fertilizers are applied, also results in a loss of nitrogen. To improve the longevity of nitrogen in the soil, fertilizers have been treated with nitrification inhibitors and urease inhibitors. These inhibitors are usually imparted onto the surface of fertilizer granules or added to liquid fertilizers through an aqueous solution.

Thus, it is desired that one increase the life expectancy of nitrogen in the soil to insure more consistent levels of nitrogen during the growing season while also decreasing the number of times the fertilizer is applied to the soil. Increasing the life expectancy of nitrogen in soil while simultaneously decreasing the number of applications of fertilizer will lower the overall cost to the agriculture industry while at the same time limiting the amount of nitrogen carried into the waterways. The present methods that are used create polluting conditions that are believed to have fueled the formation of the Gulf Dead Zone, the formation of toxic algal blooms as well as damage to drinking water supplies. Thus, finding delivery formulations that are safe for the environment and for animals and that contain the proper levels of nitrification inhibitors and/or urease inhibitors that may be applied directly to the soil in a liquid form or imparted onto fertilizer granules as a one-step application would be advantageous to the agricultural industry. Such a treated fertilizer would also assist in slowing two major biological processes that cause substantial loss of nitrogen in soil while simultaneously assisting in controlling pollution of our water and atmosphere.

DESCRIPTION OF THE RELATED ART

Various methods as disclosed in the patents below, which are incorporated by reference in their entireties, have been proposed and developed for controlling volatile nitrogen loses from urea.

Barth (U.S. Pat. No. 6,488,734) introduces the concept of the use of polyacids, which contain nitrification inhibitors, and pyrazole derivatives for the treatment of inorganic fertilizers;

Halpern (U.S. Pat. No. 5,106,984) shows how to prepare 1, 1-dichloro-2-propanone and acrylonitrile by the formation and further reaction of 4, 4-dichloro-5-oxo-hexanenitrile, which are utilized as herbicides and as a nitrification inhibitor.

Evrard (U.S. Pat. No. 4,294,604) discloses the use of selected N-(2, 6-dimethylphenyl)-alanine methyl ester compounds as ammonium nitrification inhibitors.

Michaud (U.S. Pat. No. 4,234,332) describes aqueous solutions of commonly used fertilizers which also contain dicyandiamide, in an amount to provide at least 10% by weight of dicyandiamide nitrogen which is an effective nitrification inhibitor.

Sutton et al. (U.S. Pat. No. 5,024,689) teach the use of liquid fertilizer that includes urease inhibitors such as NBPT (N-(n-butyl) thiophosphoric triamide) and nitrification inhibitor such as dicyandiamide in aqueous mixtures of urea, ammonium polyphosphate, ammonium thiosulfate and potentially other plant growth improving compounds.

Sutton (U.S. Pat. No. 8,562,711) provides a method for developing a dry, flowable additive for aqueous urea-based fertilizers based on solid urea formaldehyde polymer, N-(n-butyl) thiophosphoric triamide, and, optionally, dicyandiamide that imparts reduced nitrogen loss from the soil. Also, Sutton provides that the dry additive may be blended with molten or solid urea to form a solid urea-based fertilizer with reduced nitrogen loss from the soil.

While many of these techniques have a positive impact of maintaining the level of nitrogen in the soil, they also have significant problems. For example, problems that have adversely affected the agricultural industry include costs of improvement, loss of viability upon storage, and the inability to deliver consistent levels of fertilizer due to poor coating of the inhibitors or clumping of granules. Some innovations utilize aqueous delivery systems to granular fertilizer. However, aqueous delivery systems not only cause fertilizer to clump, but if this fertilizer has also been coated with an alkyl thiophosphoric triamide such as nBTP, the presence of moisture will cause degradation of the alkyl thiophosphoric triamide. Thus, there is a need for a composition, which addresses many of the shortcomings discussed above.

BRIEF SUMMARY OF THE INVENTION

Urea is a desirable starting material for fertilizers and fertilizer additives, which can provide high nitrogen content and can be used in fertilizer products that provide phosphorus or potassium as primary nutrients, and calcium, magnesium, or sulfur as secondary nutrients or micronutrients such as boron, copper, iron, manganese, molybdenum and zinc. These fertilizer products can deliver the nutrients to the soil and through numerous biological processes can be converted to forms that are capable of being absorbed by plants. The use of a nitrification inhibitor such as cyanoamides, typically, dicyanoamide by itself or combined with a urease inhibitor such as phosphoramides are one embodiment of the invention. In an embodiment, the present invention relates to using N-alkyl thiophosphoric triamide in combination with a cyanoamide by either blending two separate dispersions containing each material or combining the two inhibitors by dissolving them together in an organic liquid dispersing formulation. The resulting mixture can then be applied to the fertilizer, which will inhibit biological oxidation by soil microbes, such as Nitrosomonas bacteria and/or, the mixture may aid in enzymatic action of urease from ammoniacal nitrogen to nitrate nitrogen.

In one embodiment, improved delivery formulations have been developed that deliver expected and effective levels of nitrification inhibitors that increase the nitrogen longevity in the soil. It has been found that the delivery formulations of the present invention provide a liquid vehicle to deliver an even, non-clumping application of the desired inhibitors to the fertilizer granule. These new delivery formulations for nitrification inhibitors are non-water-containing organo-liquids that improve storage life of urease inhibitors such as alkyl thiophosphoric triamides over those formulations containing greater than 1% water. In fact, because of the present invention, one can now combine both nitrification and urease inhibitors in one product by either blending together the dispersions of each or by combining the dispersions of both inhibitors in the same organo-liquid delivery system.

To improve the longevity of nitrogen in the soil, it has been found that one can incorporate both a nitrification inhibitor and also a urease inhibitor to the fertilizer. The improved delivery systems of the present invention can be utilized as a vehicle to impart nitrification inhibitors such as, but not limited to 2-chloro-6-(trichloromethyl)pyridine, 4-Amino-1,2,4-6-triazole-HCl, 2,4-Diamino-6-trichloromethyltriazine CL-1580, Dicyandiamide (DCD), thiourea, 1-Mercapto-1,2,4-triazole, and 2-Amino-4-chloro-6-methylpyrimidine. The combined impact of using a nitrification inhibitor together with a urease inhibitor in solution in the improved delivery system with enhanced storage stability lowers the cost of fertilizer by utilizing a one-step application to granules and delivering optimized levels of both inhibitors improving the longevity of nitrogen in the soil.

Thus, in one embodiment, the present invention relates to improved compositions of organo-liquid ingredients in a solvating system that:

-   -   Are environmentally safe;     -   Have flashpoints above 145° F.;     -   Are inherently rated safe for contact with humans and animals;     -   Maintain the nitrification inhibitors at levels of 1-50% in         solution to storage temperatures down to at least 10° C.;     -   Provides improved even application to fertilizer granules of         nitrification inhibitors while not causing clumping of the         granules.     -   Thus, in an embodiment, the present invention relates to         improved stability of urease inhibitors, for example alkyl         thiophosphoramides in which N-(n-butyl) thiophosphoric triamide         (NBPT) is one particularly effective urease inhibitor. In one         embodiment, the present invention relates to compositions having         at least 10% greater urease inhibitor relative to those standard         solvating composition systems that contain water.

In one embodiment, it has also been discovered that while various organo-liquids might meet some of the above criteria, the delivery system of the present invention can be optimized to provide a formulation with a high concentration of inhibitors while maintaining a low chill point by combining two or more organo-liquids in a solvating system. In one embodiment, one process for preparing the formulations of the present invention is to heat the combined solvents to temperatures approaching about ˜80° C. and charging the nitrification inhibitor(s) in a combined level of 10-60% of the total formula composition, which can be dissolved in the solvent mixture with moderate agitation.

In one embodiment, the present invention relates to an effective solvent combination that comprises dimethyl sulfoxide (DMSO), which can be used in combination with another organo-liquid delivery system that has a low chill point and good solvating properties. One advantage of using DMSO is that DMSO can be a source of the important nutrient of sulfur.

DETAILED DESCRIPTION

Improved delivery formulations have been developed that deliver effective levels of nitrification inhibitors that increase the nitrogen longevity in the soil. These delivery formulations not only provide a liquid vehicle to deliver an even, non-clumping application of the desired inhibitors to the fertilizer granule, but it has been discovered that formulations based on non-aqueous solvating systems improve the storage life of the important urease inhibitors, such as alkyl thiophosphoric triamides. Alkyl thiophosphoric triamides, if present in combination with nitrification inhibitors as contained in the present formulations, have been shown to be extremely effective urease inhibitors but suffer from degradation upon storage if exposed to moisture. Thus, in one embodiment the present invention relates to compositions that are substantially free of water.

The delivery system of the present invention is based on organo-liquid delivery system(s) and can contain one or more of the following:

-   -   Nitrification inhibitor(s);     -   Urease inhibitor(s);     -   Additives such as but not limited to surfactants, buffers,         fragrance/odor masking agents, colorants, micro-nutrients,         and/or flow modifiers such as silica.

In one embodiment, the compositions of the present invention contain one or more nitrification inhibitors, and one or more urease inhibitors. These compositions optionally contain one or more of surfactants, buffers, fragrance/odor masking agents, colorants, micro-nutrients, and/or flow modifiers.

In one embodiment, the organo-liquid delivery system of the present invention or blends of organo-liquids of the present invention meet one or more of the following criteria: They are:

-   -   environmentally safe;     -   thermally safe because they have flashpoints above 145° F.;     -   inherently rated safe for contact with humans and animals;     -   able to maintain nitrification inhibitors at levels of 1-50% in         solution to temperatures down to at least 10° C. This ability         means that these compositions have relatively long storage         lives.     -   able to provide improved and even application to fertilizer         granules of nitrification inhibitors while not causing clumping         of the granules.     -   They also provide improved stability of urease inhibitors,         primarily alkyl thiophosphoramides such as N-(n-butyl)         thiophosphoric triamide (NBPT). In some embodiments, the         stability of the composition is at least 10% more relative to         known solvating systems containing water.

In one embodiment, the solvating system of the present invention is an organo-liquid or a blend of organo-liquids, which may include but are not limited to one or more of the following: Dimethyl sulfoxide, Dimethylacetamide, Dimethylformamide Hexamethylphosphoramide, propylene carbonate, ethylene carbonate, butylene carbonate, N-alkyl-2-pyrrolidone, 1,2-dimethyloxyethane, 2-methoxyethyl ether, cyclohexylpyrrolidone, ethyl lactate, and 1,3 dimethyl-2-imidazolidinone, limonene, ethylene glycol, propylene glycol, butylene glycol, trimethylol propane, pentaerythritol, glycerine, trimethylol ethane, polyethylene glycol, polypropylene glycol, polyethylene/polypropylene glycol co-polymer, Tripropylene glycol methyl ether, Tripropylene glycol butyl ether, acetate and/or fumerate capping of glycols which include but are not limited to the following glycols:

ethylene glycol, propylene glycol, butylene glycol, trimethylol propane, pentaerythritol, glycerine, trimethylol ethane, polyethylene glycol, polypropylene glycol, polyethylene/polypropylene glycol co-polymer, Tripropylene glycol methyl ether, Tripropylene glycol butyl ether.

Additionally, the delivery formulations of the present invention may contain one or more of the following:

-   -   a food coloring or dye that may be used to improve the visual         evidence of complete coverage and serve as a visual marker;     -   scents or masking agents to improve the odor of the         formulations;     -   Nonionic, anionic, cationic, zwitterionic, and/or amphoteric         surfactants to improve formula application performance of         fertilizer granules; and     -   Buffering agents.

In an embodiment, the formulation may contain one or more nitrification inhibitors. Examples of nitrification inhibitors that may be used in the present invention include but are not limited to 2-chloro-6-(trichloromethyl)pyridine, 4-Amino-1,2,4-6-triazole-HCl, 2,4-Diamino-6-trichloromethyltriazine CL-1580, Dicyandiamide (DCD), thiourea, 1-Mercapto-1,2,4-triazole and/or 2-Amino-4-chloro-6-methylpyrimidine.

In one embodiment, the formulations of the present invention may use Dicyandiamide at levels from between about 5-50% of the total composition. Using concentrations in this range gives cost effective performance and provides the secondary benefit of being a slow release fertilizer. It is believed that this is due to the relatively high 65% nitrogen content. In one embodiment, the present invention provides for compositions that are substantially free of water. These compositions provide advantages over the systems of the prior art that use water as the delivery solvent. The present invention is also advantageous relative to other systems that have used cost prohibitive coating/adhesion technologies.

In one embodiment of the present invention, the utilization of ambient temperature organic solvent systems allows for non-clumping granules. Moreover, use of these ambient temperature organic solvent systems prevents thermal degradation of these compositions. IN one embodiment, urease inhibitors such as phosphoric triamides are ideally suited for providing fertilizer systems that are not susceptible to degradation (or degradation of the fertilizer system(s) the. In one embodiment, the present invention allows for the additional benefit that coating or adhesion is not needed to maintain a consistent level of nitrification inhibitor on the fertilizer.

In an embodiment, the formulation(s) of the present invention may contain one or more nitrification inhibitors in combination with one or more urease inhibitors. Urease inhibitors can be but are not limited to phosphoric triamides. While phosphoric triamides are extremely effective, thiophosphoric triamides have longer term impact on soil nitrogen content and also contribute the primary nutrient of sulfur to the soil. The presence of an alkyl group on thiophosphoric triamides, such as n-butyl thiophosphoric triamide, improves further the urease inhibitor's longevity in the soil. In an embodiment, it has been found that effective levels of urease inhibitor in the delivery system are from about 5-50% or from about 10-50% or from about 20-40% of the total concentration of the formulation(s).

In one embodiment, the present invention relates to using a low temperature dispersion procedure (around about 10° C.) with one or more phosphoric triamides in a formulation. In one variation, this low temperature procedure and the application of the formulation to the surface of pre-formed fertilizer granules prevents thermal degradation of these phosphoric triamides.

In an embodiment, Dicyandiamide (DCD) may be incorporated in amounts that are about 10-45% of a formulation mixture that also contains DMSO and propylene glycol at ratios from about 80/20 to 20/80. In an embodiment, DCD may be added, under agitation, to the combined organic liquids that have been heated in a mixing vessel at a temperature of about 0° C. to 100° C., or alternatively to a temperature of about 40° C. to 100° C., or alternatively to a temperature of about 60° C. to 100° C., or alternatively to a temperature of about 70° C. to 100° C., and mixed until the DCD is completely dissolved. In an embodiment, the heated mix vessel may be jacketed and the temperature carefully controlled. In a variation, the mixing action allows complete mixing without too much aeration. Heating can be accomplished using hot water or low pressure steam to control any hot spots on walls of the vessel to prevent heat degradation to the DCD. Alternatively, the mixing may be done at reduced pressure to limit thermal degradation. At this stage (after the initial mixing), the mixture may be cooled to about 25° C. or below and one or more of the following may be added, if desired:

-   -   One or more urease inhibitors dispersed in an organic liquid         dispersing system;     -   a food coloring or dye to improve the visual evidence of         complete coverage and serve as a visual marker;     -   scents or masking agents to improve the odor of the formula;     -   Nonionic, anionic, cationic, zwitterionic, and/or amphoteric         surfactants to improve formula application performance of         fertilizer granules; and/or     -   Buffering agents.

In an embodiment, Dicyandiamide (DCD) may be incorporated in an amount that is between about 10-45% of the total formulation amount wherein the formulation also contains a mixture of DMSO and one or more of ethylene and or propylene glycol present at ratios between about 80/20 to 20/80. In an embodiment, DCD may be added, under agitation, to the combined organic liquids that have been heated in a mixing vessel at a temperature of about 0° C. to 100° C. or alternatively to a temperature of about 40° C. to 100° C., or alternatively to a temperature of about 60° C. to 100° C., or alternatively to a temperature of about 70° C. to 100° C., and mixed until the DCD is completely dissolved. In an embodiment, the heated mix vessel may be jacketed and the temperature carefully controlled. In a variation, the mixing action allows complete mixing without too much aeration. The heating can be accomplished using hot water or low pressure steam to control any hot spots on walls of the vessel to prevent heat degradation to the DCD. Alternatively, mixing may occur at reduced pressure. After the initial mixing has occurred, the mixture may be cooled to around about 35° C. and N-(n-butyl) thiophosphoric triamide (NBPT) can be added at about 5-45% by weight under agitation to the dissolved nitrification inhibitors and mixed until the NBPT is completely dissolved. At this stage, the mixture can be further cooled to around about 25° C. or below and one or more of the following may be added, if desired:

-   -   a food coloring or dye that improves the visual evidence of         complete coverage and serves as a visual marker;     -   scents or masking agents that improve the odor of the formula;     -   Nonionic, anionic, cationic, zwitterionic, and/or amphoteric         surfactants to improve formula application performance on         insuring even distribution and of fertilizer granules in the         soil: and/or     -   Buffering agents.

In an embodiment, one or more additional urease inhibitors and/or one or more additional nitrification inhibitors may be added to formulations of the present invention. In an embodiment, the additional urease inhibitor and/or nitrification inhibitor may be dissolved in the mixture. In an embodiment, useful mixtures may be prepared either by dilution or mixture with liquid fertilizers.

Examples of the present formulation include liquid mixtures of urea or solid mixtures that may be made by contacting the mixture with solid fertilizers such as granular urea. In an embodiment, coated granular urea can be prepared by using any commercially available equipment in which granular product can be mixed or sprayed with a liquid. A flow aid, silicas or surfactants such as soap or nonionic surfactants may be added prior to addition of the liquid for improved dispersability.

The resulting product(s) can be applied to soil in either a liquid or granular form to provide improved nitrogen retention in the soil for uptake for plant life.

In an embodiment, the present relates to a composition comprising one or more nitrification inhibitors and one or more urease inhibitors.

In one embodiment, the one or more nitrification inhibitors may be one or more of 2-chloro-6-(trichloromethyl)pyridine, 4-Amino-1,2,4-6-triazole-HCl, 2,4-Diamino-6-trichloromethyltriazine CL-1580, Dicyandiamide, thiourea, 1-Mercapto-1,2,4-triazole, and 2-Amino-4-chloro-6-methylpyrimidine.

In an embodiment, the one or more urease inhibitors may be one or more of phosphoric triamides, thiophosphoric triamides and alkylated thiophosphoric triamides, wherein the alkylated thiophosphoric triamides has one or more alkyl groups that independently contain between 1 and 6 carbon atoms.

In an embodiment, the one or more nitrification inhibitors comprises dicyanoamides and the one or more urease inhibitors comprises phosphoramides.

In an embodiment, the composition may comprise one or more of surfactants, buffers, fragrance/odor masking agents, colorants, micro-nutrients, and/or flow modifiers.

In an embodiment, the one or more nitrification inhibitors comprises dicyandiamide in a formulation wherein dicyandiamide is present in an amount that is between about 10-45% of a total formulation amount and the formulation also contains a mixture of DMSO and propylene glycol in ratios that are between about 20/80 to 80/20.

In an embodiment, the composition comprises one or more nitrification inhibitors that comprises dicyandiamide in a formulation wherein dicyandiamide is present in an amount that is between about 10-45% of a total formulation amount and the formulation also comprises N-(n-butyl) thiophosphoric triamide.

In an embodiment, the composition is substantially free of water.

In one embodiment, the composition (and the methods that use the composition and fertilizer additives) may have a solvating agent. The solvating agent may have the compounds of Formula I wherein

B—X—Y is Formula I

wherein:

B is —H, CH₃—O—, or HO—, X is —CH₂—,

or —CH₂—CH₂—

-   -   wherein W is —H, —CH₂—CH₃, or —CH₃

Y is —CH₂-A,

U, —N(CH₃)₂, or

-   -   wherein A is —OK,

-   -   wherein K is —H, —CH₃, or

-   -   wherein R⁵ is —H, —CH₃, —CH(OH)—CH₃     -   wherein L is —H, —CH₃, or

-   -   wherein “AC” is —H, —CH₃, —CH(OH)—CH₃     -   wherein a is 1-10     -   wherein M is —H, —CH₃,

-   -   -   wherein R⁶ is —H, —CH₃, —CH(OH)—CH₃

    -   wherein b is 1-10

    -   wherein Q is H, —CH₃,

-   -   -   wherein R⁷ is —H, —CH₃, —CH(OH)—CH₃

    -   wherein c is 1-10

    -   wherein d is 1-10         wherein D is —O-“AB”, (OCH₂CH₂—)_(e)O“AD”,

-   -   wherein “AB” is —H, —CH₃,

-   -   -   wherein “AG” is —H, —CH₃, —CH(OH)—CH₃

    -   wherein “AD” is —H, —CH₃,

-   -   -   wherein “AH” is —H, —CH₃, —CH(OH)—CH₃

    -   wherein e is 1-10

    -   wherein “AE” is —H, —CH₃,

-   -   -   wherein “AI” is —H, —CH₃, —CH(OH)—CH₃

    -   wherein f is 1-10

    -   wherein “AF” is —H, —CH₃,

-   -   -   wherein “AJ” is —H, —CH₃, —CH(OH)—CH₃

    -   wherein g is 1-10

    -   wherein h is 1-10         wherein J is —CH₃ or —CH₂—CH₃         wherein G is —CH₃,

wherein T is —N(CH₃)₂ wherein R¹ is —H, —OH, —CH₂OH wherein R² is —CH₃,

wherein R³ is —H, —OH, —CH₂OH wherein R⁴ is —H, —OH, —CH₂OH wherein U is —H, —CH₂—CH₃, —CH₃, —CH₂—OH.

In an embodiment, the present invention relates to fertilizer additives. In one embodiment, the fertilizer additive comprises one or more nitrification inhibitors and one or more urease inhibitors.

In an embodiment, the fertilizer additive comprises one or more nitrification inhibitors that are selected from the group consisting of 2-chloro-6-(trichloromethyl)pyridine, 4-Amino-1,2,4-6-triazole-HCl, 2,4-Diamino-6-trichloromethyltriazine CL-1580, Dicyandiamide, thiourea, 1-Mercapto-1,2,4-triazole, and 2-Amino-4-chloro-6-methylpyrimidine.

In an embodiment, the fertilizer additive comprises one or more urease inhibitors that are selected from the group consisting of phosphoric triamides, thiophosphoric triamides and alkylated thiophosphoric triamides, wherein the alkylated thiophosphoric triamides has one or more alkyl groups that independently contain between 1 and 6 carbon atoms.

In an embodiment, the fertilizer additive has one or more nitrification inhibitors that comprises dicyanoamides and one or more urease inhibitors that comprises phosphoramides.

In an embodiment, the present invention relates to making compositions and fertilizer additives. In one embodiment, the present invention relates to a method of making a composition to be added to a fertilizer, wherein the method comprises:

heating a mixture comprising one or more nitrification inhibitors and one or more urease inhibitors to effectuate mixing of the mixture;

cooling the mixture to a temperature that optionally allows addition of one or more of surfactants, buffers, fragrance/odor masking agents, colorants, micro-nutrients, and/or flow modifiers.

In one variation of the method, the method comprises further adding the composition to a fertilizer.

In one variation, the method comprises a composition that has one or more nitrification inhibitors, the one or more nitrification inhibitors being selected from the group consisting of 2-chloro-6-(trichloromethyl)pyridine, 4-Amino-1,2,4-6-triazole-HCl, 2,4-Diamino-6-trichloromethyltriazine CL-1580, Dicyandiamide, thiourea, 1-Mercapto-1,2,4-triazole, and 2-Amino-4-chloro-6-methylpyrimidine.

In one embodiment, the composition has one or more urease inhibitors. The one or more urease inhibitors are selected from the group consisting of phosphoric triamides, thiophosphoric triamides and alkylated thiophosphoric triamides, wherein the alkylated thiophosphoric triamides has one or more alkyl groups that independently contain between 1 and 6 carbon atoms.

In one embodiment, the method has a composition that comprises one or more nitrification inhibitors containing dicyanoamides and one or more urease inhibitors containing phosphoramides.

In one embodiment, the method has a composition that is substantially free of water. The following Examples are presented to illustrate certain embodiments of the present invention.

Example 1

65 grams of dimethyl sulfoxide was charged to a vessel and then placed under strong agitation and then heated to 60° C. 25 grams of dicyandiamide was then charged to the vessel and mixed until completely dissolved. Once dissolved, the mixture was cooled to 38° C. and 10 grams of tripropylene glycol methyl ether was added. The mixture was cooled to <30° C. and then packaged off in an appropriate container.

Example 2

69 grams of dimethyl sulfoxide was charged to a vessel and then placed under strong agitation and then heated to 60° C. 15 grams of dicyandiamide was then charged to the vessel and mixed until completely dissolved. Once dissolved, the mixture was cooled to 40° C. and then 10 grams of 2-chloro-6-(trichloromethyl)pyridine was as added and mixed until dissolved. 6 grams of tripropylene glycol methyl ether was added and the mixture was cooled to <30° C. and then packaged off in an appropriate container.

Example 3

65 grams of dimethyl sulfoxide was charged to a vessel and then placed under strong agitation and then heated to 80° C. 10 grams of dicyandiamide and 10 grams of thiourea were then charged to the vessel and mixed until completely dissolved. Once dissolved, the mixture was cooled to 38° C. and then 5 grams of n-butyl thiophosphoric triamide was charged to the vessel and mixed until completely dissolved. 15 grams of propylene glycol was charged to the vessel and the mixture was agitated for 30 minutes. The mixture was then cooled to <30° C. and then packaged off in an appropriate container.

Example 4

57.1 grams of dimethyl sulfoxide was charged to a vessel and then placed under strong agitation and then heated to 40° C. 20 grams of 2-chloro-6-(trichloromethyl)pyridine was then charged to the vessel and mixed until completely dissolved. Once dissolved, 22.9 grams of dipropylene glycol was charged the mixture was cooled to <30° C. and then packaged off in an appropriate container.

Example 5

58.3 grams of dimethyl sulfoxide was charged to a vessel and then placed under strong agitation and then heated to 60° C. 25 grams of 3,4-dimethylpyrazole phosphate was then charged to the vessel and mixed until completely dissolved. Once dissolved, the mixture was cooled to 38° C. and then 4.3 grams of tripropylene glycol methyl ether and 12.5 grams of propylene carbonate were charged to the vessel and the mixture was agitated for 30 minutes. The mixture was then cooled to <30° C. and then packaged off in an appropriate container.

Example 6

54.4 grams of dimethyl sulfoxide was charged to a vessel and then placed under strong agitation and then heated to 60° C. 10 grams of 2-chloro-6-(trichloromethyl)pyridine and 15 grams of thiourea were then charged to the vessel and mixed until completely dissolved. Once dissolved, the mixture was cooled to 38° C. and then 10.6 grams of dipropylene glycol and 10 grams of propylene glycol were charged to the vessel and the mixture was agitated for 30 minutes. The mixture was then cooled to <30° C. and then packaged off in an appropriate container.

Example 7

45 grams of dimethyl sulfoxide was charged to a vessel and then placed under strong agitation and then heated to 60° C. 25 grams of 1H-1,2,4-triazole thiol was then charged to the vessel and mixed until completely dissolved. Once dissolved, the mixture was cooled to 38° C. and then 30 grams of N,N-dimethyl 9-decenamide was added to the vessel and the mixture was agitated for 30 minutes. The mixture was then cooled to <30° C. and then packaged off in an appropriate container.

Example 8

50 grams of dimethyl sulfoxide was charged to a vessel and then placed under strong agitation and then heated to 60° C. 15 grams of 2-chloro-6-(trichloromethyl)pyridine was then charged to the vessel and mixed until completely dissolved. Once dissolved, the mixture was cooled to 38° C. and then 5 grams of n-butylthiophosphoric triamide was and the resulting product was mixed until dissolved. 30 grams of dipropylene glycol was charged to the vessel and the mixture was agitated for 30 minutes. The mixture was then cooled to <30° C. and then packaged off in an appropriate container.

Example 9

80 grams of dimethyl sulfoxide was charged to a vessel and then placed under strong agitation and then heated to 80° C. 20 grams of dicyandiamide was then charged to the vessel and mixed until completely dissolved. Once dissolved, the mixture was cooled to 30° C. and packaged off in an appropriate container.

Example 10

80 grams of dimethyl sulfoxide was charged to a vessel and then placed under strong agitation and then heated to 38° C. 20 grams of n-butylthiophosphoric triamide was then charged to the vessel and mixed until completely dissolved. Once dissolved, the mixture was cooled to 30° C. and packaged off in an appropriate container.

Example 11

80 grams of propylene carbonate was charged to a vessel and then placed under strong agitation and then heated to 38° C. 20 grams of n-butylthiophosphoric triamide was then charged to the vessel and mixed until completely dissolved. Once dissolved, the mixture was cooled to 30° C. and packaged off in an appropriate container.

Example 12

80 grams of tripropylene glycol methyl ether was charged to a vessel and then placed under strong agitation and then heated to 38° C. 20 grams of dicyandiamide was then charged to the vessel and mixed until completely dissolved. Once dissolved, the mixture was cooled to 30° C. and packaged off in an appropriate container.

Example 13

75 grams of dimethyl sulfoxide was charged to a vessel and then placed under strong agitation and then heated to 60° C. 25 grams of 4-amino-4H-1,2,4-triazole was then charged to the vessel and mixed until completely dissolved. Once dissolved, the mixture was cooled to 30° C. and packaged off in an appropriate container.

Example 14

50 grams of Example 9 and 50 grams of Example 10 were mixed together for 30 minutes and then packaged off in an appropriate container.

Example 15

58.3 grams of dimethyl sulfoxide was charged to a vessel and then placed under strong agitation and then heated to 60° C. 25 grams of 4-amino-4H-1,2,4-triazole was then charged to the vessel and mixed until completely dissolved. Once dissolved, the mixture was cooled to 30° C., 16.7 grams of propylene glycol was added, the formulation was mixed for 30 minutes and then packaged off in an appropriate container.

Example 16

80 grams of dipropylene glycol was charged to a vessel and then placed under strong agitation and heated to 38° C. 20 grams of 2-chloro-6-(trichloromethyl)pyridine was then charged to the vessel and mixed until completely dissolved. The mixture was cooled to 30° C. and packaged off in an appropriate container.

Example 17

50 grams of dimethyl sulfoxide was charged to a vessel and then placed under strong agitation and then heated to 80° C. 20 grams of dicyandiamide was then charged to the vessel and mixed until completely dissolved. Once dissolved, the mixture was cooled to 30° C. and 16 grams of propylene carbonate, and 14 grams of propylene glycol were charged to the vessel and then mixed for 15 minutes and packaged off in an appropriate container.

Example 18

80 grams of propylene glycol was charged to a vessel and then placed under strong agitation and then heated to 60° C. 20 grams of thiourea was then charged to the vessel and mixed until completely dissolved. The mixture was cooled to 30° C. and packaged off in an appropriate container.

Example 19

50 grams of dimethyl acetamide was charged to a vessel and then placed under strong agitation and then heated to 38° C. 20 grams of n-butylthiophosphate triamide was then charged to the vessel and mixed until completely dissolved. Once dissolved, the mixture was cooled to 30° C. and 20 grams of propylene carbonate and 10 grams of propylene glycol were charged to the vessel and mixed for 15 minutes and then packaged off in an appropriate container.

Example 20

75 grams of dimethyl sulfoxide was charged to a vessel and then placed under strong agitation and then heated to 60° C. 25 grams of 3, 4-dimethylpyrazole phosphate was then charged to the vessel and mixed until completely dissolved. Once dissolved, the mixture was cooled <30° C. and then packaged off in an appropriate container.

Example 21

75 grams of dimethyl sulfoxide was charged to a vessel and then placed under strong agitation and then heated to 60° C. 25 grams of 2-chloro-6-(trichloromethyl)pyridine was then charged to the vessel and mixed until completely dissolved. Once dissolved, the mixture was cooled <30° C. and then packaged off in an appropriate container.

The below table 1 summarizes the compositions that occur in each of the examples. The presence of an “X” in table 1 means that the particular example composition contains that particular component.

TABLE 1 Example No. DMSO DCD TPGME CTMP thiourea NBPT PG DPG DMPP PC TT DD AT DMA 1 X X X 2 X X X X 3 X X X X X 4 X X X 5 X X X X 6 X X X X X 7 X X X 8 X X X X 9 X X 10 X X 11 X X 12 X X 13 X X 14 X X X 15 X X X 16 X X 17 X X X X 18 X X 19 X X X X 20 X X 21 X X DMSO—dimethylsulfoxide TPGME—tripropylene glycol methyl ether NBPT—n-butyl thiophosphoric triamide DPG—dipropylene glycol PC—propylene carbonate DD—N,N-dimethyl 9-decenamide DMA—dimethyl acetamide DCD—dicyandiamide CTMP—2-chloro-6-(trichloromethyl)pyridine PG—propylene glycol DMPP—3,4 dimethylpyrazole phosphate TT—1H-1,2,4,-triazole thiol AT—4-amino-4H-1,2,4-triazole

Samples from Examples 1-21 were evaluated for physical properties and the results are shown in the below Table 2:

TABLE 2 Stability Aquatic Sample 24 hrs Chill Point Human Health Flash Toxicity # @ 20° C. °F. Rating Point ° F. Rating Ex 1  Stable <−5° 1.0 >145° Low Ex 2  Stable <−5° 1.0 >145° Low Ex 3  Stable <−5° 1.0 >145° Low Ex 4  Stable 23° F. 1.0 >145° Low Ex 5  Stable <−5° 1.0 >145° Low Ex 6  Stable  5° 1.0 >145° Low Ex 7  Stable  10° 2 >145° Medium Ex 8  Stable  5° 1 >145° Low Ex 9  Stable  25° 1 >145° Low Ex 10 Stable  32° 1 >145° Low Ex 11 cloudy  72° 1 >145° Low Ex 12 Not soluble N/A 1 >145° Low Ex 13 Stable 37.4 1 >145° Low Ex 14 Stable <−5° 1 >145° Low Ex 15 Stable <−5  1 >145° Low Ex 16 Not soluble N/A 1 >145° Low Ex 17 Stable <−5° 1 >145° Low Ex 18 Not soluble N/A 1 >145° Low Ex 19 Stable <−5° 3 <145° Medium Ex 20 Stable  55° 1 >145° Low Ex 21 Stable  55° 1 >145° Low

The Human Health rating is based on the HMIS (Hazardous Materials Information System) rating on Health of any organo solvent component >2%

The Flash Point is based on the flash point of any organo solvent component >5%.

The Aquatic Toxicity Rating is based on any organo solvent component at any level.

It should be apparent from the above table 2 that a combination of factors will produce an organo-liquid delivery system that provides or gives a solution that includes at least one of the following characteristics:

-   -   a. soluble     -   b. Are environmentally safe;     -   c. Have flashpoints above 145° F.;     -   d. Are inherently rated safe for contact with humans and         animals;     -   e. Maintain the nitrification inhibitors at levels of 1-50% in         solution to storage temperatures down to at least 10° C.;     -   f. Provides improved even application to fertilizer granules of         nitrification inhibitors while not causing clumping of the         granules

In an embodiment, the composition results in a formulation that satisfies more than one of the above functional properties. In a variation, the formulations may have two of the above functional properties, or alternatively, three of the above functional properties, or alternatively, four of the above functional properties, or alternatively five of the above functional properties or alternatively all six of the above functional properties. Each of the functional properties may be desired (or emphasized) relative to the other functional properties based upon the intended use and transport of the compositions of the present invention. For example, one functional property may be emphasized based upon storage conditions of the formulations, or the shipping conditions of the formulations, or how the formulation is used, or based upon some other desired property. For example, if one knows that the formulation is likely to be stored at high temperatures for a long period of time, the functional property that provides the greatest stability of the formulation is likely to be used. Environmental safety may be emphasized if the formulations of the present invention are to be used where any potential run-off of the formulation is to be used near a drinking source.

In one embodiment of the present invention, compositions were made that gave favorable properties for most of the above listed functional properties. That is, the compositions of the present invention attempted to emphasize solubility, environmental safety, a low freeze chill point, a high flash point, even coating of a fertilizer particle and a composition that could be handled safely by both humans and/or animals.

The results as shown in the above table 2 demonstrate that the usage of a single organo-liquid solvent may in some instances show a much higher chill point product versus blends of the various solvents. For example, comparing examples 4, 21 and 16 shows that a blend of DMSO with other organo-liquid solvents has a beneficial effect as it relates to the lower chill point and improving solubility. Other trends can be observed by comparing a) examples 9, example 1, example 12 and example 17, b) example 13 to example 15, and c) example 5 and example 20.

In one embodiment of the present invention, it is contemplated and therefore within the scope of the invention that compositions such as examples 2, 3 and 6 that contain more than one nitrification inhibitor will have superior performance in inhibiting the conversion of ammonia to nitrite and/nitrate over compositions containing only one nitrification inhibitor due to the expected differences in mechanisms by which each nitrification inhibitor operates, the variation of enzymatic sites and the fact that this conversion is basically orchestrated by two groups of organisms, ammonia-oxidizing bacteria (AOB) and ammonia-oxidizing archaea (AOA). The flexibility of the organo-liquid delivery system in solubilizing the various nitrification inhibitors in certain embodiments provides stable, environmentally responsible and safe compositions. Thus, in certain embodiments, these compositions can be added easily and economically to a broad range of manmade and natural fertilizers, thus improving the longevity of these applied fertilizers.

Example 22

To better visualize coating and penetration on the urea prills, Example 17 was dyed with powdered ‘Rhodamine 6G’ dye (Sigma-Aldrich). The powdered dye (20 mg) was added to 10 mL of Example 17 and mixed thoroughly. The resulting product was reddish-purple in color. It was then topically applied to granulated urea at an application rate equivalent to 3 qt/ton. The resulting product was thoroughly mixed for three minutes, providing uniform coverage to the prills. The product was then allowed to sit for 3 hours.

Eight spherical prills of relatively uniform size were selected at random from the red-dyed covered urea. The prills were split in half with a razor blade. One half of each prill was glued to a piece of paper with the split face (middle) facing up, and the prills were photographed.

The coverage on the urea prills was equally uniform as was the penetration of the wills. The average prill diameter was 3.2 mm (⅛ inch). Example 17 penetrated the prills approximately one-sixth of the diameter, or to a depth of 0.5 mm ( 1/48 inch). The penetration depth of 0.5 mm is visually demonstrated in FIG. 1. The average diameter 1 of each urea covered prill is shown in FIG. 1 as well as well as the average penetration depth 2.

Example 23

An inhibition study was conducted as described below.

Experimental Outline:

A 12 week laboratory experiment was conducted in an incubation chamber set to a constant air temperature of 85° F. The experiment consisted of 4 replicate 1 quart disposal plastic tubs, each filled with 250 grams of wetted soil (a Marvyn loamy sand, which is approximately 80% sand), each of which was submitted to the appropriate treatments. Prior to placing the soil in the jar the sample was sieved through a 2 mm screen and wetted to an uniform water content (˜70% of field capacity). The background soil sample indicated the following parameters: soil pH: 5.6, phosphorus: 15 lb/A, potassium: 32 lb/A, magnesium: 20 lb/A, and calcium: 139 lb/A. No lime or additional fertilizers were added to this soil.

The following 5 treatments were evaluated, and there were four replications of each treatment.

Sample Treatment 1 4 quarts of Example 17 per ton of urea 2 6 quarts of Example 17 per ton of urea 3 8 quarts of Example 17 per ton of urea 4 Urea only control 5 No fertilizer control

The correct amount of Example 17 to treat one pound of urea was calculated, and that amount was sprayed on to the urea using an air brush sprayer. Example 17 was not diluted, and a uniform coating was achieved. The treated (and untreated) ureas were then mixed at an N ratio of 120 pounds N/acre. The corresponding N ratio was calculated using the area of the plastic tub.

The soil-fertilizer mix was placed into the incubator. Each week thereafter (for 12 weeks) the following occurred: 1) each bin was removed from the incubator, opened and lightly mixed before sampling, 2) a 2 g subsample of soil was removed for soil-water content determination, and, 3) a 2 g subsample of soil was removed for soil nitrate and ammonium concentration (via 2M KCl extraction). The bins were resealed and returned to the incubator until the next sampling date.

Conclusions:

Application of Example 17 at 4 qt/T significantly increased soil ammonium-N at weeks 4, 5 and 6. When Example 17 was applied at 6 qt/T there was more soil ammonium-N (as compared to the urea only treatment) at weeks 3 and 6. The best inhibition of nitrification was observed when the Example 17 was applied at 8 qt/T, as soil ammonium in that treatment was greater than measured in the urea only treatment at weeks 2, 3, 4, 5, 6 and 7. This ratio gives the best inhibition of nitrification.

If nitrification is inhibited, the nitrogen content resulting from ammonium will accumulate, as the ammonium to nitrate conversion is slowed. Since nitrate-N production is slowed, the treatments to which an inhibitor should have reduced nitrate-N. This was observed when the highest rate of Example 17 was applied (8 qt/T) and the effect was significant (as compared to the urea only treatments) in weeks 4, 5, 6 and 7. When lower rates of Example 17 were applied, the effect was only significant at weeks 5 and 7.

In this one time 8 week incubation study, when Example 17 was applied to urea at 8 qt/Ton, it exhibited significant nitrification inhibitory properties.

Example 24

A degradation study was performed using 2-chloro-6-(trichloromethyl)pyridine/nBPT in DMSO.

A 2-chloro-6-(trichloromethyl)pyridine/NBPT=1/1(w/w) mixture was dissolved in DMSO. LC (liquid chromatography) was performed to analyze the content decrease versus time. All samples were sealed and protected under N₂. All samples were stored 50° C. Analysis condition:

A C18 column was used, and measured at 255 nm. Retention time: 40 min. Temperature: 30° C. 15 μL injection. Peak area percentages were calculated to analyze the concentration and are shown in below Table 3.

TABLE 3 Solvent DMSO solute 2-chloro-6- n-butylthiophosphoric (trichloromethyl)pyridine triamide Week # 1  100 100 2  99 99.6 3  99.4 98 4  98.3 97.6 6  95.3 96.5 7  93.2 95.3 8  92.3 94.7 9  90.8 93 10 88 92.2 11 86.7 92.1 12 86.4 91.7 13 85 91 14 84.33 90.88 15 83.56 90.01 16 81.45 99.55 17 81 89.06 18 80.09 88.6 Both actives show good stability in DMSO at 50° C. for 18 weeks.

In an embodiment, the present invention relates to a composition comprising one or more nitrification inhibitors and/or urease inhibitors in an organo-liquid or a blend of organo-liquids comprising but are not limited to one or more of the following:

Dimethyl sulfoxide, Dimethylacetamide, Dimethylformamide Hexamethylphosphoramide, propylene carbonate, ethylene carbonate, butylene carbonate, N-alkyl-2-pyrrolidone, 1,2-dimethyloxyethane, 2-methoxyethyl ether, cyclohexylpyrrolidone, ethyl lactate, and 1,3 dimethyl-2-imidazolidinone, limonene, ethylene glycol, propylene glycol, butylene glycol, trimethylol propane, pentaerythritol, glycerine, trimethylol ethane, polyethylene glycol, polypropylene glycol, polyethylene/polypropylene glycol co-polymer, Tripropylene glycol methyl ether, Tripropylene glycol butyl ether, acetate and/or fumerate capping of glycols which include but are not limited to the following glycols: ethylene glycol, propylene glycol, butylene glycol, trimethylol propane, pentaerythritol, glycerine, trimethylol ethane, polyethylene glycol, polypropylene glycol, polyethylene/polypropylene glycol co-polymer, Tripropylene glycol methyl ether, Tripropylene glycol butyl ether. wherein the organo-liquid delivery system meets the following criteria:

-   -   a. soluble     -   b. Are environmentally safe;     -   c. Have flashpoints above 145° F.;     -   d. Are inherently rated safe for contact with humans and         animals;     -   e. Maintain the nitrification inhibitors at levels of 1-50% in         solution to storage temperatures down to at least 10° C.;     -   f. Provides improved even application to fertilizer granules of         nitrification inhibitors while not causing clumping of the         granules

In an embodiment the composition comprises a nitrification inhibitor that is one or more of the following 1) dicyandiamide, 2) 2-chloro-6-(trichloromethyl)pyridine, 3) 4-amino-1,2,4-6-triazole-HCl, 4) 2,4-diamino-6-trichloromethyltriazine, 5) thiourea, 6) 1-mercapto-1,2,4-triazole and 2-amino-4-chloro-6-methylpyrimidine, or 7) 3,4-dimethylpyrazole phosphate.

In an embodiment, the present invention relates to a composition comprising one or more nitrification inhibitors and/or urease inhibitors in an organo-liquid or a blend of organo-liquids comprising but are not limited to one or more of the following in Formula I:

B—X—Y is Formula I

wherein:

B is —H, CH₃—O—, or HO—, X is —CH₂—,

or —CH₂—CH₂—

-   -   wherein W is —H, —CH₂—CH₃, or —CH₃

Y is —CH₂-A,

U, —N(CH₃)₂, or

-   -   wherein A is —OK,

-   -   wherein K is —H, —CH₃, or

-   -   wherein R⁵ is —H, —CH₃, —CH(OH)—CH₃     -   wherein L is —H, —CH₃, or

-   -   wherein “AC” is —H, —CH₃, —CH(OH)—CH₃     -   wherein a is 1-10     -   wherein M is —H, —CH₃,

-   -   -   wherein R⁶ is —H, —CH₃, —CH(OH)—CH₃

    -   wherein b is 1-10

    -   wherein Q is H, —CH₃,

-   -   -   wherein R⁷ is —H, —CH₃, —CH(OH)—CH₃

    -   wherein c is 1-10

    -   wherein d is 1-10         wherein D is —O-“AB”, (OCH₂CH₂—)_(e)O“AD”,

-   -   wherein “AB” is —H, —CH₃,

-   -   -   wherein “AG” is —H, —CH₃, —CH(OH)—CH₃

    -   wherein “AD” is —H, —CH₃,

-   -   -   wherein “AH” is —H, —CH₃, —CH(OH)—CH₃

    -   wherein e is 1-10

    -   wherein “AE” is —H, —CH₃,

-   -   -   wherein “AI” is —H, —CH₃, —CH(OH)—CH₃

    -   wherein f is 1-10

    -   wherein “AF” is —H, —CH₃,

-   -   -   wherein “AJ” is —H, —CH₃, —CH(OH)—CH₃

    -   wherein g is 1-10

    -   wherein h is 1-10         wherein J is —CH₃ or —CH₂—CH₃         wherein G is —CH₃,

wherein T is —N(CH₃)₂ wherein R¹ is —H, —OH, —CH₂OH wherein R² is —CH₃,

wherein R³ is —H, —OH, —CH₂OH wherein R⁴ is —H, —OH, —CH₂OH wherein U is —H, —CH₂—CH₃, —CH₃, —CH₂—OH; wherein the organo-liquid delivery system meets the following criteria:

-   -   a. soluble     -   b. Are environmentally safe;     -   c. Have flashpoints above 145° F.;     -   d. Are inherently rated safe for contact with humans and         animals;     -   e. Maintain the nitrification inhibitors at levels of 1-50% in         solution to storage temperatures down to at least 10° C.;     -   f. Provides improved even application to fertilizer granules of         nitrification inhibitors while not causing clumping of the         granules.

In one variation, the composition comprises an organo-liquid delivery system in the mixture that is dimethyl sulfoxide. In a variation, dimethyl sulfoxide comprises between about 10 and 90% of the total composition.

In one embodiment, the nitrification inhibitor(s) is/are present in an amount that is between about 5-45% of a total formulation amount and the composition also contains a mixture of DMSO and one or more organo-liquid solvents in ratios that are between about 20/80 to 80/20.

In an embodiment, the composition further comprises: surfactants, buffers, fragrance/odor masking agents, colorants, micro-nutrients, dispersed nitrification inhibitors, dispersed urease inhibitor(s), crystallization inhibitors and/or flow modifiers.

In an embodiment, the nitrification inhibitor(s) is/are present in an amount that is between about 5-45% of a total formulation amount and the formulation also comprises N-(n-butyl) thiophosphoric triamide in an amount that is between about 5-45% of the total formulation amount.

In one embodiment, the composition is substantially free of water.

In an embodiment, the present invention relates to a fertilizer granule or liquid additive, which comprises one or more nitrification inhibitors and/or urease inhibitors in an organo-liquid or a blend of organo-liquids comprising but are not limited to one or more of the following: Dimethyl sulfoxide, Dimethylacetamide, Dimethylformamide Hexamethylphosphoramide, propylene carbonate, ethylene carbonate, butylene carbonate, N-alkyl-2-pyrrolidone, 1,2-dimethyloxyethane, 2-methoxyethyl ether, cyclohexylpyrrolidone, ethyl lactate, and 1,3 dimethyl-2-imidazolidinone, limonene, ethylene glycol, propylene glycol, butylene glycol, trimethylol propane, pentaerythritol, glycerine, trimethylol ethane, polyethylene glycol, polypropylene glycol, polyethylene/polypropylene glycol co-polymer, Tripropylene glycol methyl ether, Tripropylene glycol butyl ether, acetate and/or fumerate capping of glycols which include but are not limited to the following glycols:

-   -   ethylene glycol, propylene glycol, butylene glycol, trimethylol         propane, pentaerythritol, glycerine, trimethylol ethane,         polyethylene glycol, polypropylene glycol,         polyethylene/polypropylene glycol co-polymer, Tripropylene         glycol methyl ether, Tripropylene glycol butyl ether.

In an embodiment, the fertilizer granule or liquid additive comprises one or more nitrification inhibitors such as 1) dicyandiamide, 2) 2-chloro-6-(trichloromethyl)pyridine, 3) 4-amino-1,2,4-6-triazole-HCl, 4) 2,4-diamino-6-trichloromethyltriazine, 5) thiourea, 6) 1-mercapto-1,2,4-triazole and 2-amino-4-chloro-6-methylpyrimidine, or 7) 3,4 dimethylpyrazole phosphate.

In a variation, the fertilizer granule or liquid additive may further comprise one or more urease inhibitors such as phosphoric triamides, thiophosphoric triamides or alkylated thiophosphoric triamides, wherein the alkylated thiophosphoric triamides have one or more alkyl groups that independently contain between 1 and 6 carbon atoms.

In an embodiment, the fertilizer granule or liquid additive may contain one or more nitrification inhibitors such as 1) dicyandiamide, 2) 2-chloro-6-(trichloromethyl)pyridine, 3) 4-amino-1,2,4-6-triazole-HCl, 4) 2,4-diamino-6-trichloromethyltriazine, 5) thiourea, 6) 1-mercapto-1,2,4-triazole and 2-Amino-4-chloro-6-methylpyrimidine, or 7) 3,4 dimethylpyrazole phosphate; wherein the one or more urease inhibitors comprises phosphoramides.

In an embodiment, the present invention relates to making the compositions and fertilizer granules and liquid additives of the present invention. In one variation, the method relates to making a composition to be added to a fertilizer comprising:

heating a mixture comprising one or more nitrification inhibitors in an organo liquid delivery system comprising an organo-liquid or a blend of organo-liquids comprising but are not limited to one or more of the following:

Dimethyl sulfoxide, Dimethylacetamide, Dimethylformamide Hexamethylphosphoramide, propylene carbonate, ethylene carbonate, butylene carbonate, N-alkyl-2-pyrrolidone, 1,2-dimethyloxyethane, 2-methoxyethyl ether, cyclohexylpyrrolidone, ethyl lactate, and 1,3 dimethyl-2-imidazolidinone, limonene, ethylene glycol, propylene glycol, butylene glycol, trimethylol propane, pentaerythritol, glycerine, trimethylol ethane, polyethylene glycol, polypropylene glycol, polyethylene/polypropylene glycol co-polymer, Tripropylene glycol methyl ether, Tripropylene glycol butyl ether, acetate and/or fumerate capping of glycols which include but are not limited to the following glycols:

-   -   ethylene glycol, propylene glycol, butylene glycol, trimethylol         propane, pentaerythritol, glycerine, trimethylol ethane,         polyethylene glycol, polypropylene glycol,         polyethylene/polypropylene glycol co-polymer, Tripropylene         glycol methyl ether, Tripropylene glycol butyl ether. and         cooling the mixture to a temperature that optionally allows an         addition of one or more of:     -   surfactants, buffers, fragrance/odor masking agents, colorants,         micro-nutrients, dispersed nitrification inhibitors, dispersed         urease inhibitor(s), crystallization inhibitors and/or flow         modifiers.

In a variation, the method further comprises adding the composition to a fertilizer granule or liquid as an additive.

In one variation, the method makes a composition wherein the one or more nitrification inhibitors is selected from the group consisting of 1) dicyandiamide, 2) 2-chloro-6-(trichloromethyl)pyridine, 3) 4-amino-1,2,4-6-triazole-HCl, 4) 2,4-diamino-6-trichloromethyltriazine, 5) thiourea, 6) 1-mercapto-1,2,4-triazole and 2-amino-4-chloro-6-methylpyrimidine, and 7) 3,4 dimethylpyrazole phosphate.

In one variation, the method uses one or more urease inhibitors selected from the group consisting of phosphoric triamides, thiophosphoric triamides and alkylated thiophosphoric triamides, wherein the alkylated thiophosphoric triamides have one or more alkyl groups that independently contain between 1 and 6 carbon atoms.

In one variation, the method uses one or more nitrification inhibitors such as 1) dicyandiamide, 2) 2-chloro-6-(trichloromethyl)pyridine, 3) 4-amino-1,2,4-6-triazole-HCl, 4) 2,4-diamino-6-trichloromethyltriazine, 5) thiourea, 6) 1-mercapto-1,2,4-triazole and 2-amino-4-chloro-6-methylpyrimidine, 7) 3,4 dimethylpyrazole phosphate; and the one or more urease inhibitors comprises phosphoramides.

In one variation of the method, the method employs steps so as to make sure that the composition is substantially free of water.

The following references are incorporated by reference in their entireties.

-   U.S. Pat. No. 4,234,332 to Michaud -   U.S. Pat. No. 4,294,604 to Evrard -   U.S. Pat. No. 5,024,689 to Sutton et al. -   U.S. Pat. No. 5,106,984 to Halpern -   U.S. Pat. No. 6,488,734 to Barth -   U.S. Pat. No. 8,562,711 to Sutton, and -   WO 2008/000196.

It is contemplated and therefore within the scope of the present invention that any feature that is described above can be combined with any other feature that is described above. When mixtures, formulations and/or compositions are discussed, it should be understood that those mixtures, formulations and/or compositions are contemplated as being parts of bigger mixtures, formulations and/or compositions. It is also contemplated that any feature or member of a group can be omitted from a list of possible features and/or members. Further, if a composition is enumerated, methods using and methods of making that composition are contemplated and within the scope of the present invention. When a range is discussed, it is contemplated and therefore within the scope of the invention that any number that falls within that range is contemplated as an end point generating a plurality of sub-ranges within that range. For example if a range of 1-10 is given, 2, 3, 4, 5, 6, 7, 8, and 9 are contemplated as end points to generate a sub-range that fit within the scope of the enumerated range. Moreover, it should be understood that the present invention contemplates minor modifications that can be made to the compositions and methods of the present invention. In any event, the present invention is defined by the below claims. 

1. A fertilizer composition comprising a. urea, b. one or more nitrification inhibitors selected from the group consisting of 2-chloro-6-(trichloromethyl)pyridine, 4-Amino-1,2,4-6-triazole-HCl, 2,4-Diamino-6-trichloromethyltriazine CL-1580, thiourea, 1-Mercapto-1,2,4-triazole, 2-Amino-4-chloro-6-methylpyrimidine, and dicyandiamide, c. one or more members selected from the group consisting of a) propylene glycol, b) glycerin and c) polyethylene glycol, d. N-alkyl-2-pyrrolidone, e. and optionally, a dye/colorant, wherein said one of more nitrification inhibitors are delivered to a surface of the urea as a completely dissolved, non-aqueous, liquid formulation.
 2. The fertilizer composition of claim 1, wherein said one or more nitrification inhibitors comprise 2-chloro-6-(trichloromethyl)pyridine.
 3. The fertilizer composition of claim 1, wherein the one or more nitrification inhibitors comprises dicyandiamide.
 4. The fertilizer composition of claim 1, wherein said dye/colorant provides visual confirmation a) that said one or more nitrification inhibitors have been delivered as an even coating on the urea and b) that penetration of the urea has occurred.
 5. The fertilizer composition of claim 1, wherein the fertilizer composition further comprises one or more urease inhibitors selected from the group consisting of a) phosphoric triamides, b) thiophosphoric triamides and c) alkylated thiophosphoric triamides, wherein the alkylated thiophosphoric triamides have one or more alkyl groups that independently contain between 1 and 6 carbon atoms, and wherein said one or more urease inhibitors are delivered to the surface of urea as a completely dissolved non-aqueous, liquid formulation.
 6. The fertilizer composition of claim 5, wherein said one or more urease inhibitors comprise N-(n-butyl) thiophosphoric triamide.
 7. The fertilizer composition of claim 1, wherein the fertilizer composition further comprises one or more members selected from the group consisting of a) surfactants, b) buffers, c) fragrance/odor masking agents, d) micro-nutrients, and e) flow modifiers.
 8. The fertilizer composition of claim 1, wherein the fertilizer composition further comprises one or more members selected from the group consisting of a) one or more alkylene carbonates selected from the group consisting of i) propylene carbonate, ii) ethylene carbonate, and iii) butylene carbonate, b) cyclohexylpyrrolidone, c) ethyl lactate, d) 1,3 dimethyl-2-imidazolidinone, e) limonene, f) one or more polyols selected from the group consisting of i) ethylene glycol, ii), butylene glycol, iii) trimethylol propane, iv) pentaerythritol, v) trimethylol ethane, vi) polypropylene glycol, and vii) polyethylene/polypropylene glycol co-polymer, g) tripropylene glycol methyl ether, h) tripropylene glycol butyl ether, i) acetate and/or fumerate capping of one or more members selected from the group consisting of (i) propylene glycol, (ii) butylene glycol, (iii) polyethylene glycol, (iv) tripropylene glycol methyl ether, and (v) tripropylene glycol butyl ether, and j) dimethyl sulfoxide.
 9. The fertilizer composition of claim 1, wherein the fertilizer composition further comprises dimethyl sulfoxide.
 10. The fertilizer composition of claim 1, wherein the fertilizer composition further comprises water.
 11. A fertilizer composition comprising a. an aqueous mixture of urea, b. one or more nitrification inhibitors selected from the group consisting of 2-chloro-6-(trichloromethyl)pyridine, 4-Amino-1,2,4-6-triazole-HCl, 2,4-Diamino-6-trichloromethyltriazine CL-1580, thiourea, 1-Mercapto-1,2,4-triazole, 2-Amino-4-chloro-6-methylpyrimidine, and dicyandiamide, c. one or more members selected from the group consisting of a) propylene glycol, b) glycerin and c) polyethylene glycol, d. N-alkyl-2-pyrrolidone, e. and optionally a dye/colorant, wherein said one of more nitrification inhibitors are delivered to said aqueous mixture of urea as a completely dissolved, non-aqueous, liquid formulation.
 12. The fertilizer composition of claim 11, wherein said one or more nitrification inhibitors comprises 2-chloro-6-(trichloromethyl)pyridine.
 13. The fertilizer composition of claim 11, wherein the one or more nitrification inhibitors comprises dicyandiamide.
 14. The fertilizer composition of claim 11, wherein the fertilizer composition further comprises one or more urease inhibitors selected from the group consisting of a) phosphoric triamides, b) thiophosphoric triamides and c) alkylated thiophosphoric triamides, wherein the alkylated thiophosphoric triamides have one or more alkyl groups that independently contain between 1 and 6 carbon atoms, and wherein said one or more urease inhibitors are delivered to the aqueous mixture of urea as a completely dissolved, non-aqueous, liquid formulation.
 15. The fertilizer composition of claim 14, wherein said one or more urease inhibitors comprise N-(n-butyl) thiophosphoric triamide.
 16. The fertilizer composition of claim 11, wherein the fertilizer composition further comprises one or more members selected from the group consisting of a) surfactants, b) buffers, c) fragrance/odor masking agents, d) micro-nutrients, and e) flow modifiers.
 17. The fertilizer composition of claim 11, wherein the fertilizer composition further comprises one or more members selected from the group consisting of a) one or more alkylene carbonates selected from the group consisting of i) propylene carbonate, ii) ethylene carbonate, and iii) butylene carbonate, b) cyclohexylpyrrolidone, c) ethyl lactate, d) 1,3 dimethyl-2-imidazolidinone, e) limonene, f) one or more polyols selected from the group consisting of i) ethylene glycol, ii), butylene glycol, iii) trimethylol propane, iv) pentaerythritol, v) trimethylol ethane, vi) polypropylene glycol, and vii) polyethylene/polypropylene glycol co-polymer, g) tripropylene glycol methyl ether, h) tripropylene glycol butyl ether, i) acetate and/or fumerate capping of one or more members selected from the group consisting of (i) propylene glycol, (ii) butylene glycol, (iii) polyethylene glycol, (iv) tripropylene glycol methyl ether, and (v) tripropylene glycol butyl ether, and j) dimethyl sulfoxide.
 18. The fertilizer composition of claim 11, wherein the fertilizer composition further comprises dimethyl sulfoxide.
 19. The fertilizer composition of claim 4, wherein said penetration of the urea is approximately one-sixth of a diameter of the urea after three hours.
 20. A fertilizer composition comprising a. urea, b. one or more nitrification inhibitors selected from the group consisting of 2-chloro-6-(trichloromethyl)pyridine, 4-Amino-1,2,4-6-triazole-HCl, 2,4-Diamino-6-trichloromethyltriazine CL-1580, thiourea, 1-Mercapto-1,2,4-triazole, 2-Amino-4-chloro-6-methylpyrimidine, and dicyandiamide, c. dimethyl sulfoxide, d. N-alkyl-2-pyrrolidone, e. and optionally, a dye/colorant, wherein said one of more nitrification inhibitors are delivered to a surface of the urea as a completely dissolved, non-aqueous, liquid formulation. 